JPH10120962A - Oil based ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil based ink composition having excellent drying characteristics of a print, distinct stamping characteristics to a stamping surface which has low absorptivity, usable as a stamping ink free from decreasing of the stamping characteristics while opening the stamping ink bed for a long time, as a marking ink from inhibition of writing caused by dry up of the penpoint, in addition, as an ink for a ballpoint pen having excellent drying characteristics and free from troubles of bleeding of ink on the adhered as a ink for an ink jet, etc. SOLUTION: This ink composition consists of 20-95wt.% of a solvent comprising at least one selected from among alcohols, ethers, esters having vapor pressure of 0.005-45mmHg at 20 deg.C, and having 13.0-20.0 of variance term δd , 1.0-10.0 of polarity term δp and, 5.0-20.0 of hydrogen bond term δh in Hansen's three dimensional solubility parameter, 0.001-10wt.% of an additive agent suppressing solvent vaporization containing ester derivatives of polyvalent alcohols, 0.001-30wt.% of at least one kind of additives selected from a group consisting of solvent soluble resins and surfactants, and 1-50wt.% of coloring agents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ink for stamping,
The present invention relates to an oil-based ink composition used for recording inks such as ink jet inks, writing inks such as ballpoint pen inks and marking pen inks.

[0002]

2. Description of the Related Art Conventionally, inks for writing implements and recording inks are roughly classified into water-based inks and oil-based inks. For example, in the case of ink used on a stamp board, the water-based ink is mainly used to penetrate the paper surface and dry before being applied. Low speed and very poor drying. Also, when a large amount of water-based ink adheres to the rubber stamp surface, the ink has poor drying properties due to the poor wettability of the ink on the rubber stamp surface.
Imprints tend to blur. Conversely, if the amount of ink adhering to the rubber stamp surface is controlled to a small amount, the ink becomes sparse and the imprint at the time of stamping becomes dirty. Further, the water-based ink has a disadvantage that water resistance is poor due to the use of a water-soluble dye. On the other hand, there are two types of oil-based inks for stamps, a type using a non-volatile solvent and a type using a highly volatile solvent, both of which have very good water resistance. However, the former type has the advantage that it is not necessary to keep the stamp stand in a closed state at all times because of its low volatility, but since it is applied to paper or the like mainly by penetration-drying like water-based ink, There is a drawback that imprints imprinted on non-absorbing surfaces such as paper and coated paper have low drying properties. The latter type is
There is an advantage that the ink imprinted on the non-absorbing surface has a high drying property because the ink adheres to the paper surface mainly by evaporation-drying. However, since the ink contains an extremely volatile solvent, the ink adhesion amount on the rubber stamp surface must be increased in order to prevent drying. As a result, the imprint by stamping lacks sharpness due to excessive ink adhesion. In addition, because of the high volatility of the ink, if the lid of the stamp ink stand is left open for a while, the surface of the board will dry and the amount of ink attached will be extremely reduced, making the imprint faint or impossible to print. There is. In the case of marking pen ink, oil-based ink is used as an ink that can be written on both absorbent surfaces such as paper and cloth and non-absorbent surfaces such as plastic, glass and metal. If removed and left, the ink will dry and solidify, and the ink components will precipitate on the pen tip, etc., reducing the ink supply and preventing the ink from flowing out of the pen tip. There are problems such as dry-up. Other ballpoint pen inks and ink jet inks have similar problems.

[0003]

SUMMARY OF THE INVENTION As described above, the present invention aims to solve the problems relating to the drying properties of oil-based inks used for writing implement inks and recording inks and the bleeding of ink-coated surfaces. . For example, in the case of stamp ink, good dryness of imprinting by stamping, clear marking performance, performance to suppress the drying of the board surface of the stamp ink stand, and printing on hardly absorbing ink printing surfaces such as art paper and coated paper It has excellent drying properties and gives clear imprints on thin and coarse fibrous paper surfaces such as tracing paper, and does not impair the printing performance even when the lid of the stamp ink stand is open for a long time. It is an object to provide an oil-based ink composition. Further, in the case of a marking ink, it is another object of the present invention to provide an oil-based ink composition that does not cause writing failure due to dry-up with a pen tip. Further, there is a similar problem with ballpoint pen ink and ink for ink jet.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a solvent having a limited vapor pressure and a three-dimensional Hansen three-dimensional dissolution parameter and a polyvalent additive as an additive having an evaporation suppressing effect are provided. The inventors have found that the above-mentioned problems can be solved by using an ester derivative of an alcohol, and have completed the oil-based ink composition of the present invention.

The oil-based ink composition of the present invention has a vapor pressure at 20 ° C. of 0.005 to 45 mmHg and a dispersion term δ _d of 13.0 in a Hansen three-dimensional dissolution parameter.
20.0, polarity term [delta] _p is from 1.0 to 10.0, a hydrogen bond term [delta] _h alcohols having a value of 5.0 to 20.0,
Ether, a solvent comprising at least one selected from esters, a solvent evaporation suppressing additive containing an ester derivative of a polyhydric alcohol, at least one additive selected from the group consisting of a resin soluble in the solvent and a surfactant , And a colorant. Preferably, the ester derivative of the polyhydric alcohol is at least one selected from polyglycerin higher fatty acid esters having an HLB of 2.0 to 16.0. Further, based on the total amount of the composition, the solvent is 20 to 95% by weight, the solvent evaporation suppressing additive is 0.001 to 10% by weight, and the additive is 0.001 to 3% by weight.
0% by weight and 1 to 50% by weight of a coloring agent.

The stamp ink, writing implement ink and ink jet ink of the present invention are characterized by containing the oil-based ink composition.

[0007] The stamp ink stand of the present invention is filled with the oil-based ink composition. The pen for writing implement of the present invention,
It is filled with the oil-based ink composition.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The solvent used in the oil-based ink composition of the present invention has a vapor pressure at 20.degree.
5 mmHg, the dispersion term δ _d is 13.0 to 20.0, and the polarity term δ _p is 1.
It is a solvent comprising at least one selected from alcohols, ethers and esters having a value of 0 to 10.0 and a hydrogen bond term δ _h of 5.0 to 20.0. For example, alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and the like having two or more carbon atoms in the molecule, ethylene glycol, diethylene glycol, 3-methyl-1,3
Butanediol, triethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,5-pentanediol, hexylene glycol, two or more carbons in a molecule such as octylene glycol, Polyhydric alcohols having two or more hydroxyl groups are exemplified.

Examples of ethers include dialkyl ethers such as methyl isopropyl ether, diethyl ether, ethyl propyl ether, ethyl butyl ether, 2-ethylhexyl ether, diisopropyl ether, dibutyl ether and dihexyl ether;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monobutyl ether,
Diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether,
Tripropylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol tertiary butyl ether, propylene glycol phenyl ether, 3-methyl-3-
And glycol ethers such as methoxy-1-butanol.

The esters include, for example, methyl formate, ethyl formate, propyl formate, isobutyl formate,
Isoamyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate,
Isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, isobutyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl isobutyrate, ethyl isobutyrate,
Fatty acid esters such as propyl isobutyrate, and glycol esters such as propylene glycol methyl ether acetate, propylene glycol diacetate, 3-methyl-3-methoxybutyl acetate, propylene glycol ethyl ether acetate, and ethylene glycol ethyl ether acetate. These alcohols, polyhydric alcohols, ethers, esters and the like may be used alone or in combination of two or more.

[0011] The content of these solvents in the oil-based ink composition of the present invention is in the range of 20 to 95% by weight, preferably 30 to 90% by weight, more preferably 40 to 90% by weight.

The solvent evaporation suppressing additive used in the oil-based ink composition of the present invention always contains an ester derivative of a polyhydric alcohol. The polyhydric alcohol ester derivative preferably has an HLB value of 2.0 to 16.0 and is selected from the group consisting of polyglycerin higher fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester and propylene glycol fatty acid ester. And fatty acid esters of polyhydric alcohols. More preferred are polyglycerin higher fatty acid esters, and very effective particularly when polyglycerin stearate ester is used. . In addition, as a solvent evaporation suppression additive other than these, acidic phosphoric acid higher alcohol esters or salts thereof, phosphite higher alcohol esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides and the like are also mentioned. Although it has a small evaporation suppressing effect, it may be used in combination with an ester derivative of a polyhydric alcohol. The HLB of the ester derivative of the polyhydric alcohol is in the range of 2.0 to 16.0, preferably 2.0 to 14.0, and more preferably 2.0 to 1.
When the range is 3.0, the effect of suppressing the evaporation of the solvent is good. The solvent evaporation suppressing additives used in the present invention may be used alone or in combination of two or more. Further, its content is 0.001 to 10% by weight in the composition, preferably 0.0 to 10% by weight.
05 to 5% by weight, more preferably 0.01 to 5% by weight
It is.

Examples of polyglycerin higher fatty acid esters include glyceryl monostearate, glyceryl monooleate, diglycerin monostearate, diglycerin monolaurate, diglycerin monopalmitate, diglycerin monooleate, diglycerin sesquiolate, Diglycerindiolate, diglycerin monoisopalmitate, diglycerin monoisostearate,
Diglycerin diisostearate, diglycerin triisostearate, triglycerin monolaurate, triglycerin monostearate, triglycerin monooleate, triglycerin monoisostearate, triglycerin diisostearate, tetraglycerin monocaprylic acid Ester, tetraglycerin monolaurate, tetraglycerin monostearate, tetraglycerin tristearate, tetraglycerin pentastearate, tetraglycerin monooleate, tetraglycerin pentaolate, tetraglycerin monoisostearate, pentaglycerin monolaurate, penta Glycerin monooleate, pentaglycerin monoisostearate, hexaglycerin monomyristate, hexaglycerin monooleate, Kisa glycerol dioleate, hexaglycerin penta oleate, hexaglycerin monostearate, hexaglycerin hexastearate, hexaglycerol sesquistearate, hexaglycerol distearate, hexaglycerol tristearate,
Hexaglycerin pentastearate, hexaglycerin monocaprylate, hexaglycerin monolaurate, hexaglycerin monoisostearate, octaglycerin monostearate, octaglycerin monooleate, decaglycerin monocaprylate, decaglycerin monomyristate, Decaglycerin monooleate, decaglycerindiolate, decaglycerin triolate, decaglycerin tetraolate, decaglycerin pentaolate, decaglycerin hexaolate, decaglycerin heptaolate, decaglycerin octarate, decaglycerin decaolate, decaglycerin monostearate , Decaglycerin distearate, decaglycerin tristearate, decaglycerin pentastearate Decaglycerol hepta stearate, decaglycerol octa stearate, decaglycerol deca stearate, decaglycerol monolaurate,
Examples include decaglycerin monopalmitate, decaglycerin heptabehenate, decaglycerin monolinoleate, and decaglycerin diisostearate. Particularly, polyglycerin stearate is preferred.

Examples of the sorbitan fatty acid ester include sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitandiolate, sorbitan triolate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan sesquisteare Rate, sorbitan sesquiolate, sorbitan monositol oil fatty acid ester, sorbitan sesquitol oil fatty acid ester, sorbitan monoisostearate and the like.

Examples of the sucrose fatty acid esters include, for example, sucrose laurate, sucrose myristate, sucrose palmitate, and sucrose oleate. Examples of the propylene glycol fatty acid ester include propylene glycol monolaurate, propylene glycol monomyristate, propylene glycol monooleate, propylene glycol monostearate, propylene glycol dilaurate, propylene glycol dimyristate, propylene glycol distearate, and the like. .

The colorant used in the oil-based ink composition of the present invention mainly includes a dye and a pigment. The dye is not particularly limited as long as it is soluble in the above-mentioned solvent in an amount of 3.0% by weight or more. Direct dyes, acid dyes, basic dyes, mordant / acid mordant dyes, azoic dyes, sulfur / sulfide vat dyes, vat dyes, disperse dyes, oil-soluble dyes, food dyes, metals used in ordinary dye ink compositions Complex salt dyes and the like. As the pigment, any one of inorganic and organic pigments used in ordinary pigment ink compositions can be used. The content of the colorant in the oil-based ink composition of the present invention is in the range of 1 to 50% by weight, preferably 2 to 40% by weight, and more preferably 2 to 35% by weight.
It is. 2 to 25% by weight for dyes, 5 for pigments
A range of ~ 35% by weight is preferred.

The resin in the at least one additive selected from the group consisting of the resin and the surfactant used in the composition of the present invention may be any resin as long as it is soluble in the above solvent in an amount of 3.0% by weight or more. Well, for example, glue, gum arabic, natural resins such as rosin, hydroxyethyl cellulose and its derivatives, semi-synthetic resins such as rosin derivatives, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl ether, styrene-maleic acid copolymer, ketone Resin, styrene
A synthetic resin such as an acrylic acid copolymer can be used. These resins may be used in combination of two or more. Its content ranges from 0.5 to 30% by weight relative to the composition,
Preferably 1.0 to 20% by weight, more preferably 1.
5 to 18% by weight. These resins exhibit the effect of strengthening the seal imprint and adjusting the viscosity of the stamp ink. However, when a pigment is used as a colorant, they may be used for the purpose of a pigment dispersant.

When a pigment is used as a colorant in the composition of the present invention, a dispersant is required. The type of the dispersant may be a synthetic resin, an anionic surfactant, a cationic resin, Surfactants, surfactants such as amphoteric surfactants, and among the highly effective dispersants, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl butyral described as the above resin,
Polyvinyl ether, styrene-maleic acid copolymer,
Synthetic resins such as ketone resins and styrene-acrylic acid copolymers can be mentioned. The content of the surfactant in the oil-based ink composition of the present invention is 0.001 to 30% by weight.
, Preferably 0.01 to 25% by weight, more preferably 0.05 to 20% by weight.

When a pigment is used, the pigment can be dispersed and mixed by, for example, a method using a ball mill, a sand mill, a bead mill, a roll mill, a homomixer, a stirrer, or ultrasonic waves.

The surfactant used in the stamp ink composition of the present invention includes, as nonionic surfactants, polyoxyalkylene higher fatty acid esters, higher fatty acid partial esters of polyhydric alcohols, and higher fatty acid esters of sugars. Specifically, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, Polyoxyethylene alkyl ether, polyoxyethylene phytosterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl Phenyl ethers, polyoxyethylene castor oil, polyoxyethylene lanolin, polyoxyethylene lanolin alcohols, polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides,
And polyoxyethylene alkylphenyl formaldehyde condensate.

Examples of the anionic surfactant include an alkylated sulfonate and an alkylallyl sulfonate of a higher fatty acid amide. Specific examples thereof include alkyl sulfate, polyoxyethylene alkyl ether sulfate, and N-
Examples include acyl amino acid salts, N-acylmethyl taurine salts, polyoxyethylene alkyl ether acetates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, and the like. The surfactant is used not only as a pigment dispersant, but also as a penetrating agent for paper, to suppress bleeding of imprints, or as a surface tension modifier.

The oil-based ink composition of the present invention may further contain, if necessary, commonly used additives such as a preservative, a rust preventive, a lubricant, an antistatic agent, a defoaming agent, and the like. Can be.

[0023]

The oil-based ink composition of the present invention, when used as a stamp ink, has good drying properties for imprinting even on ink hardly-absorbable surfaces such as art paper and coated paper. Even when printing on a paper surface having such a thin and coarse fibrous material, a clear imprint is given, and even if the lid of the stamp stand is opened for a long time, the ink printing performance on the printing surface is not impaired and the printing performance is not impaired.
Also, when used as a marking ink, even if the cap etc. are left unattended, ink components do not precipitate on the pen tip, so writing performance is good, drawing lines are blurred and writing is impossible. The conventional problems that occur are not caused. Furthermore, a stamp ink stand using the ink containing the oil-based ink composition of the present invention, a pen for writing implements, marking by ink jet, writing, imprinting by printing,
Draw lines and records are robust and have good water resistance. The following can be considered as reasons why the oil-based ink composition of the present invention exhibits the above-described effects. For example,
In the case of stamp ink, since the solvent has a relatively high permeability to the printing surface and has a higher vapor pressure than the solvent of the conventional ink, when the ink is applied to the printing surface, it is dried after penetration and applied. Since two routes can be taken, i.e., evaporating, drying, and applying, the drying property is extremely improved even on a hardly absorbing surface such as art paper and coated paper. Also,
Due to the good wettability of the solvent on the rubber stamp surface and the effect of suppressing the evaporation of the ester derivative of the polyhydric alcohol, it is not necessary to adhere a large amount to the rubber stamp surface when used in stamping ink, etc. Even if the ink amount is controlled, the ink does not adhere sparsely, and as a result, the imprint due to the excessive ink does not blur and the imprint due to the controlled ink amount is not blurred, so that the imprint by the seal becomes clear . Furthermore, even if the lid of the ink stamp stand is left open for a while, the board surface does not dry out and the amount of ink collected does not drop extremely, so that the imprint is blurred or it becomes impossible to print. Never. In the case of the marking ink, there is little drying due to the evaporation of the solvent, so that the solidification does not occur and the phenomenon that the ink component is deposited on the pen tip does not occur. Furthermore, since it does not contain water-soluble materials, it can be used for stamping, writing,
Imprints, lines and records by printing are robust and have good water resistance.

In the present invention, the Hansen three-dimensional dissolution parameter indicates the following contents. First, the dissolution parameter is expressed as a measure of the miscibility between the components when mixing and dissolving, and the dissolution is expressed as follows. When the two components, component I and component II, dissolve, and the heat balance is considered as if the bond between II and II-II is changed to I-II between each molecule, each molecule surrounds it. Since releasing from the intermolecular force of molecules means vaporization, the change in internal energy when the vaporized substances are mixed and aggregated as it is is expressed by the following equation. _{ΔE = ΔE 1 + ΔE 2 -2} (ΔE 1 · ΔE 2) 0.5 ΔE = ^{_{[(ΔE 1) 0.5 - (ΔE}} 2) 0.5 ] ² [Delta] E _1; internal energy change when the components I vaporized, Delta] E ₂ A change in internal energy when the component II is vaporized, (ΔE ₁ · ΔE ₂ ) ^0.5 ; energy recovered by the binding energy generated between I and II], ie, (ΔE ₁ ) ^0.5 − (ΔE ₂ ) ^0.5 is smaller,
The enthalpy change ΔH of dissolution is small and easy to dissolve.
When ΔE per unit volume of each component is referred to as cohesion energy, ΔE is enthalpy of evaporation ΔH _V and ΔH = ΔE +
Because of the relationship of RT, Cla
ΔH is obtained by the usius-Clapeyron equation, and ΔE can be known. Here, the square root of the cohesive energy density is called a dissolution parameter and is represented by the following equation. δ = (ΔE / V) ^0.5 [ΔE; molecular cohesion energy (cal / mol), V: molecular volume (ml / mol)] There are various methods for obtaining the value, and a slightly different value is obtained depending on the measurement method or calculation method. Have been. Specific examples thereof include a latent heat of vaporization method (Hildebrand method), a vapor pressure method (Hoy method), a dissolution method, a swelling method, a surface tension method, a critical pressure method, a thermal expansion coefficient method, and a molecular attraction constant method.

The three-dimensional dissolution parameter used here is the dispersion state (London force) in the intermolecular force with respect to ΔE shown in the above equation.
An attempt was made to quantify it by dividing it into contribution rates of the dipole force (Kesom force) and the hydrogen bonding force. Representative of these are Hansen's three-dimensional dissolution parameters. The three-dimensional solubility parameter indicates ΔE as the sum of the following three components. _{ΔE = ΔE d + ΔE p +} ΔE h [ΔE _d, ΔE _p, ΔE _h respectively show dispersion force, polarity effects, hydrogen bonding results. δ is also divided into three components and is represented by the following equation. The method of dividing δ ² = δ _d ² + δ _p ² + δ _h ² δ into the above equation is as follows. δ _d ; δ of a compound (hydrocarbon) whose size and structure are similar to the target molecule and whose intermolecular force can be ignored except for the dispersive force is δ _d . δ _h ; hydrogen bond of alcoholic OH ... H is 5 × 10 ³
Since alcohol has an energy of cal / mol, δ _h = (5000 A / V _m ) ^1/2 A; number of hydroxyl groups in one molecule, V _m ; molecular volume δ _p ; Δ _d , obtained as
obtained from δ _h. It can also be obtained from the dipole efficiency and the dielectric constant. Here, “cal / mol” is used as the unit of energy, but the Hansen three-dimensional dissolution parameter shown in the claims and the like is expressed as “J / mo” in the unit of energy.
l ”, the unit is“ J / cm ³ ” ^1/2
It is expressed by

In the present invention, HLB means the following. HLB was proposed by Mr. Griffin in consideration of the balance between the strength of the hydrophilic group and the lipophilic group constituting the surfactant, and HLB was obtained from Hydrophile-Lipophile Balance.
It was named LB. Griffin proposed a formula for calculating the HLB of a nonionic surfactant, and the polyhydric alcohol fatty acid ester was represented by the following formula. HLB = 20 (1−S / A) (where A is the neutralization value of the raw material fatty acid, S is the saponification value of the ester) Those for which the saponification value is difficult to obtain are expressed by the following formula. HLB = (E + P) / 5 (where E is the weight percentage of ethylene oxide and P is the weight percentage of polyhydric alcohol) The ethylene oxide derivative of a monohydric alcohol is represented by the following formula. HLB = E / 5 In addition to the HLB obtained as described above, Kawakami proposed HLB, Moore, HLF (Hydrophile-Lipophile Factor) announced by Mr. Bell, Davies
There is an HLB of a type in which a numerical value is set to a hydrophilic group and a lipophilic group and set as a radix. In addition, the organic conceptual diagram published by Mr. Fujita is a value that considers the balance between hydrophilicity and lipophilicity. These values have different values depending on the method, but can be applied to the value of HLB described in claim 3. Here, HLB of Griffin was used as a representative value.

[0027]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. % Represents% by weight. The vapor pressure of the solvent is 20 ° C
Is the value of The δ _d value, δ _p value, and δ _h value represent the dispersion term, the polar term, and the hydrogen bond term in the Hansen three-dimensional solubility parameter.

Example 1 Colorant: oil-soluble dye “Varifast Black # 3820” manufactured by Orient Chemical Industry Co., Ltd. 8% Resin: “Ketone resin K90” manufactured by Arakawa Chemical Industry Co., Ltd.) 5% Solvent: dipropylene glycol monomethyl ether 55% (vapor pressure; 0.45 mmHg δ _d value; 15.5, δ _p value; 4.0, δ _h value; 11.5) propylene glycol monobutyl ether 30% (vapor pressure: 0.60 mm Hg δ _d value; 14.9, δ _p value; 2.4, δ _h value; 10.7) Ester derivative of polyhydric alcohol: Diglycerin monostearate (HLB = 6.5) 2% or more was obtained to obtain an oil-based ink composition. The oil-based ink composition was used as a stamp ink, which was filled in a stamp felt to prepare a stamp ink stand.

(Example 2) Colorant: oil-soluble dye [same as in Example 1] 8% Resin: polyvinyl butyral ["BL-1" manufactured by Sekisui Chemical Co., Ltd.] 5% Solvent: propylene glycol mono Butyl ether 20% (vapor pressure; 0.60 mmHg δ _d value; 14.9, δ _p value; 2.4, δ _h value; 10.7) Dipropylene glycol monomethyl ether 52% (vapor pressure: 0.45 mm Hg δ _d value; 15.5, δ _p value; 4.0, δ _h value; 11.5) 3-methoxy-3-methyl-1-butanol 10% (vapor pressure; 0.50 mmHg δ _d value; 16.0, δ _p value; 5.1, δ _h value; 12.3) Esters of polyhydric alcohol Derivative: Propylene glycol monostearate (HLB = 3.5) 2% Hexaglycerin hexastearate (HLB = 12.2) 3% An oil-based ink composition was obtained by blending at least 3%. The obtained oil-based ink composition was used as a stamp ink, and this was filled into a stamp felt to prepare a stamp ink stand.

(Example 3) Colorant: oil-soluble dye [same as in Example 1] 8% Resin: ketone resin [same as in Example 1] 3% Solvent: hexylene glycol 82% (vapor pressure: 0.02 mmHg) δ _d value; 15.7, δ _p value; 8.4, δ _h value; 17.8) Ester derivative of polyhydric alcohol: propylene glycol monostearate (HLB = 3.5) 3% hexaglycerin distearate (HLB = 8.6) 2) Surfactant: Polyether-modified silicone oil An oil-based ink composition was obtained by mixing 2% or more. The obtained oil-based ink composition was used as a stamp ink, and this was filled into a stamp felt to prepare a stamp ink stand.

Example 4 Colorant: oil-soluble dye “Varifast Black # 3830” manufactured by Orient Chemical Industries, Ltd. 8% Resin: polyvinyl butyral [same as in Example 2] 5% Solvent: diethylene glycol monobutyl ether 62% (vapor pressure; 0.01 mmHg [delta] _d values; 16.0, [delta] _p value; 7.0, [delta] _h value; 10.6) 3-methoxy-3-methyl-1-butanol 22% (vapor pressure; 0.50mmHg δ _d value ; 16.0, [delta] _p value; 5.1, [delta] _h value; 12.3) of the polyhydric alcohol ester derivatives: diglycerol monostearate (HLB = 6.5) 1.5% hexaglycerol hexastearate (HLB = 12.2) An oil-based ink composition was obtained with a mixing ratio of 1.5% or more, and the obtained oil-based ink composition was used as a stamp ink, which was filled in a stamp felt to prepare a stamp ink stand.

(Example 5) Colorant: oil-soluble dye [same as in Example 4] 8% Resin: polyvinyl butyral [same as in Example 2] 5% Solvent: dipropylene glycol monomethyl ether 51% (vapor pressure) ; 0.45mmHg δ _d value; 15.5, [delta] _p value; 4.0, [delta] _h value; 11.5) 3-methoxy-3-methyl-1-butanol 33% (vapor pressure; 0.50mmHg δ _d value; 16.0, [delta] _p value; 5.1, [delta] _h value; 12.3) of the polyhydric alcohol ester derivatives: diglycerol monostearate (HLB = 6.5) 1.5% hexaglycerol hexastearate (HLB = 12.2) 1.5% or more formulation Thus, an oil-based ink composition was obtained. The obtained oil-based ink composition was used as a stamp ink, and this was filled into a stamp felt to prepare a stamp ink stand.

Example 6 Colorant: oil-soluble dye [same as in Example 4] 8% Resin: polyvinyl butyral [same as in Example 2] 5% Solvent: hexylene glycol 52% (vapor pressure: 0.02 mmHg [delta] _d values; 15.7, [delta] _p value; 8.4, [delta] _h value; 17.8) diethylene glycol monobutyl ether 31% (vapor pressure; 0.01 mmHg [delta] _d values; 16.0, [delta] _p value; 7.0, [delta] _h value; 10.6) polyhydric Ester derivative of alcohol: diglycerin monostearate (HLB = 6.5) 1.5% Propylene glycol monostearate (HLB = 3.5) 1% Surfactant: polyether-modified silicone oil 1.5% or more An oil-based ink composition was obtained by blending. The obtained oil-based ink composition was used as a stamp ink, and this was filled into a stamp felt to prepare a stamp ink stand.

(Example 7) Colorant: carbon black [Mitsubishi Kasei Co., Ltd. "# 25"] 8% Resin: polyvinyl butyral [same as in Example 2] 5% Solvent: hexylene glycol 62% ( vapor pressure; 0.02 mmHg [delta] _d values; 15.7, [delta] _p value; 8.4, [delta] _h value; 17.8) 3-methoxy-3-methyl-1-butanol 23% (vapor pressure; 0.50mmHg δ _d value; 16.0, [delta] _p value; 5.1, [delta] _h value; 12.3) of the polyhydric alcohol ester derivatives: hexaglycerin distearate (HLB = 8.6) 1.5% decaglycerol penta stearate (HLB = 6.4) 0.5% or more To obtain an oil-based ink composition. The obtained oil-based ink composition was used as a stamp ink, and this was filled into a stamp felt to prepare a stamp ink stand.

(Comparative Example 1) Colorant: water-soluble dye "Water Black R-500" manufactured by Orient Chemical Co., Ltd. 8% Resin: polyvinylpyrrolidone ["K-30" manufactured by ISP. PET. LTD. ] 5% solvent: 30% water (vapor pressure; 17.5mmHg δ _d value; 19.5, [delta] _p value; 17.8, [delta] _h value; 17.6) glycerin 50% (vapor pressure; 0.01 mmHg [delta] _d values; 17.4, [delta] _p value; 12.1, [delta] _h value;. 29.3) to give the ink composition by the above blending the resulting ink composition and stamp ink, to produce a stamp ink pad and charged into a felt for a stamp.

(Comparative Example 2) Colorant: oil-soluble dye [same as in Example 4] 8% Resin: ketone resin [same as in Example 1] 5% Solvent: tripropylene glycol methyl ether 20% (vapor pressure; 0.02 mmHg [delta] _d values; 15.1, [delta] _p value; 3.5, [delta] _h value; 11.5) polypropylene glycol (molecular weight 1000) 67% (vapor pressure; 0.001 mmHg or less δ _d, δ _p, δ _h value is unknown) or more An ink composition was obtained by blending. The obtained ink composition was used as a stamp ink, and this was filled into a felt for stamping to prepare a stamp ink stand.

Comparative Example 3 Colorant: oil-soluble dye [same as in Example 1] 8% Resin: ketone resin [same as in Example 1] 3% Solvent: methyl alcohol 89% (vapor pressure: 100 mmHg δ _d) value; 15.1, [delta] _p value; 12.3, [delta] _h value; to give the ink composition by 22.3) above formulation. The obtained ink composition was used as a stamp ink, and this was filled into a felt for stamping to prepare a stamp ink stand.

Comparative Example 4 Colorant: oil-soluble dye [same as in Example 1] 8% Resin: polyvinyl butyral [same as in Example 2] 5% Solvent: propylene glycol monobutyl ether 35% (vapor pressure; 0.60mmHg δ _d value; 14.9, [delta] _p value; 2.4, [delta] _h value; 10.7) dipropylene glycol monomethyl ether 32% (vapor pressure; 0.45mmHg δ _d value; 16.0, [delta] _p value; 7.0, [delta] _h value; 10.6 3) 3-methoxy-3-methyl-1-butanol 20% (vapor pressure; 0.50 mmHg δ _d value; 16.0, δ _p value; 5.1, δ _h value; 12.3) An ink composition was obtained by the above composition. The obtained ink composition was used as a stamp ink, and this was filled into a felt for stamping to prepare a stamp ink stand.

Comparative Example 5 Colorant: oil-soluble dye [same as in Example 1] 8% Resin: polyvinyl butyral [same as in Example 2] 5% Solvent: propylene glycol monobutyl ether 30% (vapor pressure; 0.60mmHg δ _d value; 14.9, [delta] _p value; 2.4, [delta] _h value; 10.7) dipropylene glycol monomethyl ether 22% (vapor pressure; 0.45mmHg δ _d value; 16.0, [delta] _p value; 7.0, [delta] _h value; 10.6 15% 3-methoxy-3-methyl-1-butanol (vapor pressure; 0.50 mmHg δ _d value; 16.0, δ _p value; 5.1, δ _h value; 12.3) Ester derivative of polyhydric alcohol: diglycerin monostearate (HLB = 6.5) An ink composition was obtained by blending 20% or more. The obtained ink composition was used as a stamp ink, and this was filled into a felt for stamping to prepare a stamp ink stand.

Comparative Example 6 Colorant: oil-soluble dye [same as in Example 1] 7% Resin: ketone resin [same as in Example 1] 3% Solvent: hexylene glycol 88% (vapor pressure: 0.02 mmHg) δ _d value; 15.7, δ _p value; 8.4, δ _h value; 17.8) Ester derivative of polyhydric alcohol: polyoxyethylene nonyl phenyl ether 2% or more was used to obtain an ink composition. The obtained ink composition was used as a stamp ink, and this was filled into a felt for stamping to prepare a stamp ink stand.

Comparative Example 7 Colorant: oil-soluble dye [same as in Example 1] 8% Resin: polyvinyl butyral [same as in Example 2] 5% Solvent: propylene glycol monobutyl ether 35% (vapor pressure; 0.60mmHg δ _d value; 14.9, [delta] _p value; 2.4, [delta] _h value; 10.7) 20% dipropylene glycol monomethyl ether (vapor pressure; 0.45mmHg δ _d value; 16.0, [delta] _p value; 7.0, [delta] _h value; 10.6 ) 3-methoxy-3-methyl-1-butanol 30% (vapor pressure; 0.50 mmHg δ _d value; 16.0, δ _p value; 5.1, δ _h value; 12.3) Ester derivative of polyhydric alcohol: decaglycerin monooleate ( (HLB = 20) An ink composition was obtained by blending 2% or more. The obtained ink composition was used as a stamp ink, and this was filled into a felt for stamping to prepare a stamp ink stand.

Comparative Example 8 Colorant: oil-soluble dye [same as in Example 1] 8% Resin: ketone resin [same as in Example 1] 3% Solvent: hexylene glycol 84% (vapor pressure: 0.02 mmHg) [delta] _d values; 15.7, [delta] _p value; 8.4, [delta] _h value; 17.8) of the polyhydric alcohol ester derivatives: to give the ink composition by diglycerol tetraoleate (HLB = 1.5) 2% or more compounding. The obtained ink composition was used as a stamp ink, and this was filled into a felt for stamping to prepare a stamp ink stand.

(Comparative Example 9) Colorant: carbon black [same as in Example 7] 8% Resin: polyvinyl butyral [same as in Example 2] 5% Solvent: hexylene glycol 65% (vapor pressure: 0.02 mmHg) δ _d value; 15.7, δ _p value; 8.4, δ _h value; 17.8) 3-methoxy-3-methyl-1-butanol 24% (vapor pressure; 0.50 mmHg δ _d value; 16.0, δ _p value; 5.1, δ) _h value: 12.3) An ink composition was obtained by the above composition. The obtained ink composition was used as a stamp ink, and this was filled into a felt for stamping to prepare a stamp ink stand.

The ink composition obtained as described above was filled in a stamp pad as stamp ink, and
Imprint on paper, art paper, coated paper, glass surface, tracing paper surface, and dry, bleed,
The board dryness was tested. The results are shown in Table 1.

Evaluation of drying property: Each test surface shown above was stamped, and one hour later, PPC paper was placed on the imprint and 5
After a load of 00 g was applied, the degree of transfer to PPC paper was sensorially evaluated according to the following criteria. Those that were not transferred were rated as 、, those that were slightly transferred were rated as Δ, and those that had severe transfer phenomena were rated X.

Evaluation of bleeding of imprint: The degree of bleeding of the imprinted seal was evaluated using PPC paper and tracing paper.
One day later, the sensory evaluation was performed according to the following criteria. When no bleeding appeared in the imprint, it was evaluated as ○, when bleeding appeared in the imprint, as △, and when bleeding was severe in the imprint, as x.

Evaluation of board surface dryness: The substrate was left for 10 hours with the lid of a stamp base filled with a predetermined ink opened under the conditions of a temperature of 25 ° C. and a humidity of 65%. Then, it was stamped on PPC paper and the state of the imprint was evaluated. If it was equivalent to the initial state by the time of the third seal imprint, it was evaluated as ○, ○ if the fading phenomenon occurred, as ×.

[0048]

[Table 1]

(Example 8) Colorant: oil-soluble dye [same as in Example 4] 7% Resin: ketone resin [same as in Example 1] 2% Solvent: propylene glycol monomethyl ether 59% (vapor pressure: 0.60) mmHg; [delta] _d values; 15.6, [delta] _p value; 7.2, [delta] _h value; 13.6) ethanol 30% (vapor pressure; 44mmHg δ _d value; 15.8, [delta] _p value; 8.8, [delta] _h value; 19.4) of a polyhydric alcohol Ester derivative: Diglycerin monostearate (HLB = 6.5) An oil-based ink composition was obtained by blending 2% or more. The obtained oil-based ink composition was used as a marking ink, which was filled in a fiber bundle to prepare a marking pen. After the cap of the marking pen was removed and left for 5 hours, writing was performed. Smooth writing was possible, and a clear drawing was obtained, and no rubbing occurred.

Comparative Example 10 Colorant: oil-soluble dye [same as in Example 4] 7% Resin: ketone resin [same as in Example 1] 2% Solvent: propylene glycol monomethyl ether 61% (vapor pressure: 0.60) mmHg; [delta] _d values; 15.6, [delta] _p value; 7.2, [delta] _h value; by 19.4) above formulation; 13.6) ethanol 30% (vapor pressure; 44mmHg δ _d value; 15.8, [delta] _p value; 8.8, [delta] _h value An ink composition was obtained. The obtained ink composition was used as a marking ink, which was filled into a fiber bundle to prepare a marking pen. When writing was performed after removing the cap of the marking pen for 5 hours and leaving it, writing blurred.

[0051]

The oil-based ink composition of the present invention, when used as a stamp ink, has good drying properties of imprints imprinted on ink hardly-absorbable surfaces such as art paper and coated paper, and is suitable for tracing paper. Even when imprinting on paper with thin and coarse fibrous material such as etc., it gives a clear imprint, and even if the lid of the stamp stand is opened for a long time, the ink adhesion to the rubber stamp surface is not changed and the printing performance is impaired. Absent. Also, when used as a marking ink, the ink does not dry and solidify due to the evaporation of the solvent even if the cap etc. is left unattended, so the ink smoothly flows out of the pen tip and the writing line is blurred And excellent writing performance can be obtained. Furthermore, stamping, writing, and imprinting, drawing, and recording by using a stamp ink stand, writing instrument pen, ink jet, or the like using the ink containing the oil-based ink composition of the present invention are robust and have good water resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 11/02 B43K 8/02 F

Claims (9)

[Claims] 1. A vapor pressure at 20 ° C. of 0.005 to 4
5 mmHg, the dispersion term δ _d in the Hansen three-dimensional solubility parameter is 13.0 to 20.0, and the polarity term δ _p is 1.
0 to 10.0, a solvent composed of at least one selected from alcohols, ethers, and esters having a hydrogen bond term δ _h of 5.0 to 20.0, and solvent evaporation suppression including an ester derivative of a polyhydric alcohol. An oil-based ink composition comprising an additive, at least one additive selected from the group consisting of a resin soluble in the solvent and a surfactant, and a colorant. 2. The ester derivative of a polyhydric alcohol is H
The oil-based ink composition according to claim 1, wherein LB is from 2.0 to 16.0. 3. The oil-based ink composition according to claim 2, wherein the ester derivative of the polyhydric alcohol is at least one selected from polyglycerin higher fatty acid esters. 4. The composition according to claim 1, wherein said solvent is 20 to
95% by weight, the solvent evaporation suppressing additive 0.001 to 10
The oil-based ink composition according to any one of claims 1 to 3, comprising 0.001 to 30% by weight of the additive, and 1 to 50% by weight of the colorant. 5. An ink for stamp containing the oil-based ink composition according to claim 1. 6. An ink for writing implements comprising the oil-based ink composition according to claim 1. 7. An ink jet ink comprising the oil-based ink composition according to claim 1. 8. A stamp ink stand filled with the oil-based ink composition according to claim 1. 9. A pen for a writing implement filled with the oil-based ink composition according to claim 1.